β-Substituted Copper Porphyrin Cations: A_2u or A_1u Radicals?

Authors

Meng-Sheng Liao, Utah State University
Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Journal/Book Title/Conference

Chemical Physics Letters

Volume

367

Issue

1-2

Publisher

Elsevier BV

Publication Date

1-2-2003

First Page

199

Last Page

206

Abstract

DFT calculations have been performed on a series of β-substituted copper porphyrins, CuP–X, with particular regard to substituent effects upon the relative energies of two frontier occupied, nearly degenerate a_2u and a_1u orbitals. Substitution by electron-withdrawing groups only slightly enlarges the a_2u–a_1u separation of CuP. Electron-donating groups CH₂OH and OCH₃ raise the energies of a_2u and a_1u uniformly. In contrast, SH and NH₂ reverse the normal ordering; these [CuP–X]⁺ cation radicals are mainly a_1u in character. Electronic structures of CuP derivatives substituted at all eight β-pyrrole positions are also examined.

Recommended Citation

Meng-Sheng Liao, Steve Scheiner, β-Substituted copper porphyrin cations: A2u or A1u radicals?, Chemical Physics Letters, Volume 367, Issues 1-2, 2003, Pages 199-206, ISSN 0009-2614, https://doi.org/10.1016/S0009-2614(02)01700-1.